Catalytic Nitrate and Nitrite Reduction with Pd−Cu/PVP Colloids in Water: Composition, Structure, and Reactivity Correlations

A set of bimetallic Pd−Cu/PVP (PVP = poly(N-vinylpyrrolidone)) colloids, with copper proportions ranging from 0 to 50 atom %, has been examined as catalysts in a batch reactor with flowing hydrogen for the reduction of aqueous nitrate and/or nitrite. The encapsulated Pd−Cu nanoparticles were characterized by powder XRD, TEM, EDX, and IR of adsorbed CO. A significant decrease in average particle diameter and changes in the Pd−Cu crystallinity occurred above ca. 30% copper content, and this transition corresponded with a significant increase in observed nitrate reduction rates. The strong dependence on composition suggests that specific Cu n ensembles on the surface of the Pd−Cu nanoparticles are needed for effective nitrate-to-nitrite conversion. In contrast, nitrite reduction rates were only minimally enhanced by the presence of copper. Increasing pH had little effect on the nitrate reduction rates, but it strongly inhibited the rate of nitrite reduction. The requisite protonation of a palladium−nitrite surface intermediate is proposed.